Anthraquinone dyestuffs

ABSTRACT

THIS INVENTION CONCERNS ANTHRAQUINONE DYESTUFFS OF THE FORMULA   A(-NH-CH=C(-CN)-CO-N(-R1)-R2)N   WHEREIN A IS AN ANTHRAQUINONE RADICAL, N IS AN INTEGER FROM 1 TO 4 AND R1 AND R2 COMPLETE THE RESIDUE OF ALIPHATIC OF HETEROCYCLIC AMINES. THE DYESTUFFS ARE PREPARED BY REACTION OF THE APPROPRIATE CYANOACETIC ACID AMIDE WITH N-ANTHRAQUINONYL-N-FORMAMIDIUM SALTS. THESE DYESTUFFS ARE USEFUL FOR DYING OR PRINTING OF TEXTILES.

United States Patent )1 3,560,491 Patented Feb. 2, 1971 lice 3,560,491 ANTHRAQUINONE DYESTUFFS Riitger Neelf, Leverkusen, Germany, assignor to Farbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed July 10, 1967, Ser. No. 651,980 Claims priority, application Germany, July 16, 1966, F 49,712 Int. Cl. C07c 97/12 US. Cl. 260-240 13 Claims ABSTRACT OF THE DISCLOSURE This invention concerns anthraquinone dyestuffs of the formula wherein A is an anthraquinone radical, n is an integer from 1 to 4 and R and R complete the residue of aliphatic or heterocyclic amines. These dyestuffs are prepared by reaction of the appropriate cyanoacetic acid amide with N-anthraquinonyl-N'-formamidium salts. These dyestuffs are useful for dyeing or printing of textiles.

This invention comprises new and valuable anthraquinone dyestuffs, and the production and use thereof.

According to this invention there are provided new anthraquinone dyestuffs corresponding to the formula:

in which A stands for an anthraquinone radical; R and R stand for hydrogen, alkyl, aryl, or alkylene when employed with N and with -2 additional heteroatoms from the group O, N, and S to form a cyclic structure, x is an anion and n is an integer from 1 to 4.

The N-anthraquinonyl-N'-amidinium salts used in the process of the invention may contain in the anthraquinone radical, besides the grouping one or more substituents, for example, halogen atoms, such as fluorine, chlorine or bromine; hydroxy groups;

alkoxy groups with 1 to 6 carbon atoms; amino groups; acylamino groups; alkylamino groups with 1 to 3 carbon atoms; cycloalkylamino groups; arylamino groups wherein the aryl radical is preferably a phenyl group which may be substituted by one or more halogen atoms; alkyl or alkoxy groups; alkylor optionally substituted phenylsulphonyl groups; mercapto groups; alkylor optionally substituted phenyl-thioether radicals; cyano, carboxyl, carboxylic acid ester and acetyl groups; alkylor optionally substituted phenylsulphonylamino groups or optionally substituted sulphonamide groups. Examples of tetracyclic anthraquinone radicals are 1,9-isothiazole-anthrone, 1,9-anthrapyrimidine, 1,9-pyrazoleanthrone or N-methyl- 1,9-anthrapyridone.

The type of anion of the N-anthraquinonyl-N-amidinium salts used according to the invention is of no importance for the condensation with cyanoacetic acid amides. The anion may be a halogen ion, such as a chlorine or bromine ion, a nitrate, sulphate, phosphate, boron tetrafiuoride, benzene-sulphonate, toluene-sulphonate, oxalate or succinate anion.

The nature of of the group of the amidinum salts is likewise of no importance for the condensation with cyanoacetic acid amides. The radicals R and R are preferably hydrogen or lower alkyl radicals each which contains, for example, up to 6 carbon atoms and which may be linked with one another, optionally via heteroatoms, such as O, N, =NI-I or S. If R and/or R are aryl radicals, these may be optionally substituted phenyl radicals which contain, for example, halogen, such as C1 or Br or lower alkyl radicals, such as methyl, ethyl and propyl radicals as substituents.

Accordingly, the

group can be, for example, an amino, methylamino, ethylamino, methyl-ethylamino, phenylamino, phenyl-methylamino, diethylamino, dipropylamino, pyrrolidino, piperidino, morpholino or, preferably, a dimethylamino group. Examples of N-anthraquinonyl-N-formamidinium salts used according to the invention are the following compounds:

The cyanoacetic acid amides employed to prepare the novel anthraquinone dyestuffs of this invention have the formula:

O, N and S to form a cyclic structure; R in addition to the above, stands for aryl or a heterocyclic radical. Examples of such amides are the unsubstituted cyanoacetic acid amide, the methyl-, ethyl-, propyl-, isopropyl-, butyl-, isobutyl-, tert.-butyl-, amyl-, isoamyl, or hexylamide; the dimethyl-, methyl-ethyl-, dipropyl-, diethyl-, diisopropyl-, dibutyl-amide; the 2-chloro-, 2-bromo-, 2- fluoro-, 2-hydroxy-, 2-ethoxy-, 2-propoxy or Z-cyanoethyl-amide; the bis-(2-chloro-ethyl)-, -(2 hydroxyethyl)-, -(2-methoxyethyl)-, (2-etl1oxy ethyl-), -(2-cyanoethyl) amide; the 2-acetoxyethyl-, or Z-methoxy carbonyloxyethylamide; the bis-(2 acetoxyethyl)-amide; the bis-(2- methoxy-carbonyloxy-ethyl)-amide; the (2 acetoxyethyl)-(2 cyauoethyl) amide; the ethyl-(2-cyanoethyl)- amide; the (Z-methoxy-carbonyloxy-ethyl)(Z-cyanoethyl) amide; the methoxycarbonyl methylamide; the 2- methoxycarbonyl-ethylamide; the 3-chloro-, 3-hydroxy-, 3- methoxyor 3-ethoxy-propylamide; the bis-(3-hydroxypropyl)-amide; the 4-hydroxyor 4-methoxy-butylamide; the bis-(4-methoxybutyl)-amide; the w-hydroxy-, w-methoxyor w-ethoxy-B-ethylenoxyethyl-amide; the bis-(whydroxyor w-methoxy-fl-ethylenoxyethyl)-amide; the cyclohexyl-, 4-methylor 4-hydroxy-cyclohexylamide; the pyrrolidide, piperidide, morpholide, thiomorpholide, piperazide or N'-methylor N'-ethyl-piperazide; the vinylor allyl-amide; the bis-(vinyl)- or bis-(,B-aIIyD-amide; the phenyl-ethenylamide; the benzyl-, 4-chlorobenzyl-, 3-meth- 0xybenzyl-, 4-ethoxycarbonyl-benzylor 3-cyanobenzylamine; the bis- (benzyl)-amide; the B-phenylethylor 5-4- methoxyphenylethylamide; the 'y-phenylpropylamide; the anilide, N-methyl-anilide, 4-toluidide, N-ethyl-anilide or -p-toluidide; the 3,5-dimethylphenylamide; the 2,4,6-triethylpheuylamide; the 4 t-butylanilide; the 4-chloro-, 4- bromoor 3-fluoro-anilide; the 3,4-dichlorophenylamide; the 4-anisidide; the 2,5-dimethoxyphenylamide; the 3,4- methylene-dioxyphenylamide; the N methyl-4-anisidide; the 4-ethoxy-, 4-propoxyor 3-butoxy-anilide; the 4-methoxy or 4-ethoxy-methylphenylamide; the 3- 8-methoxy or 3-18-ethoxy ethylphenylamide; the 4-'y-methoxyor 4-'y-ethoxypropylphenylamide; the 4-methoxy-, 4-ethoxyor 4-propoxymethoxyphenylamide; the 3 methoxyor 3ethoXy-ethoxypheny1amide; the 3 ethoxycarbonyl-, 4- methoxycarbonylor 4 propoxycarbonyl-phenylamide; the 4-methoxy-carbonyl-methylphenylamide; the 3-methoxycarbonyl ethylphenylamide; the 4 ethoxycarbonylmethoxyphenylamide; the 3 methoxycarbonylaminophenylamide; the 4-methylsulphonyl phenylamide; the 4-methyl-, 4-ethy1- or 4-phenyl-thiophenylamide; the 3- or 4-pyridylamide; the 3-sulphonamido-phenylamide.

The process can be carried out by condensing the N- anthraquinonyl-N'-formamidinium salts with cyanoacetic acid amides at 0-250 C. in the presence of an acid-binding agent; it is possible to use equivalent amounts of the reaction components or an excess of the cyanoacetic acid amides and acid-binding agents. It is expedient to use organic solvents as reaction medium, for example alcohols, such as ethanol, propanol or ethylene glycol; ether alcohols, such as glycol monomethyl ether or diethylene glycol monomethyl ether; ethers such as dibutyl ether; esters, such as glycol monomethyl ether acetate; carboxylic acid amides, such as dimethy formamide, dialkyl sulphoxides or sulphones, such as dimethyl sulphoxide or tetramethylene sulphone; ketones such as butanone- (2); or hydrocarbons, such as benzene, toluene, chlorobenzene, o-dichlorobenzene or nitrobenzene.

Suitable acid-binding agents are, for example, oxides, hydroxides or salts of alkali metals or alkaline earth metals with weak inorganic or organic acids, such as calcium oxide, sodium or potassium hydroxide, sodium or potassium carbonate, sodium or ammonium hydrogen carbonate, sodium or potassium acetate, and also tertiary organic bases, such as triethylamine, N,N-dimethyl-aniline, pyridine, picoline or quinoline, or organic metal compounds such as sodium methylate or sodium ethylate.

Another method of carrying out the process consists in converting amino-anthraquinones in known manner in a suitable solvent into the N-anthraquinonyl-N-formamidinium salts mentioned above and condensing the latter, without isolation, with cyanoacetic acid amides in the presence of acid-binding agents. The dyestuffs are thus obtained in a very simple manner and in high yields.

The process according to the invention preferably yields dyestuffs which correspond to the formula in which A stands for a anthraquinone radical; R and R stand for hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, and alkylene when employed together with N and with -2 additional heteroatoms from the group O, N and S to form a cyclic structure; R in addition to the above, stands for aryl or a heterocyclic radical, and n is an integer from 1 to 4.

If R and R stand, for alkyl groups, those are preferred which contain 1 to 6 carbon atoms and may be substituted by one or more substituents of the following type: halogen atoms; hydroxy group which may be acylated by aliphatic carboxylic acids or carbonic acid semiesters; alkoxy, hydroxy-alkyleneoxy, alkoxyalkyleneoxy, alkoxycarbonyl or cyano groups. Example of these optionally substituted alkyl groups are the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, amyl, isoamyl and hexyl groups; the 2-c-hloro-, 2-bromo-, 2-fluoro-, 2-hydroxy-, 2- methoxy-, Z-ethoxyand 2-cyano-ethyl radicals; the acetoxy-ethyl radical; the methoxy-carbonyloxy ethyl group; the ethoxy-carbonylmethyl and methoxy-carbonylethyl radicals; the 3-chloro-, 3-hydroxy-, 3-methoxyand 3- ethoxy-propyl groups; the 4-methoxy-butyl radical; the hydroxy-, methoxyor ethoxy-ethyleneoxy ethyl groups. Examples of cycloalkyl groups are cyclopentyl, cyclohexyl or 4-methylcyclohexyl groups.

If R and R are alkylene groups which are linked with one another, optionally with 0-2 heteroatoms, i.e. O, N, or S, to form a heterocyclic structure with the amido ni trogen, R and R will preferably be alkylenes of 1-6 methylene groups. The resulting heterocyclic structure may, for example, be pyrrolyl, imidazolyl, imidazolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, oxazolinyl, thiazolinyl, oxadiazolyl, triazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperidinyl, triazinyl, oxazinyl, morpholinyl, thiazinyl, benzopyrrolyl, benzimidazolyl, benzthiazolyl, quinolinyl, quinoxalinyl.

If R and R are alkenyl groups, these preferably comprise the vinyl, propenyl-(l) or propenyl-(2) groups or a phenyl-ethenyl radical. If R and R stand for aralkyl groups, these are preferably benzyl, ,B-phenylethyl or 'yphenylpropyl radicals which may be substituted by halogen atoms, lOWer alkyl, alkoxy, carboxyalkyl or cyano groups.

If R; stands for an aryl radical, this is preferably an unsubstituted or a monoor polysubstituted phenyl radical which may be substituted by substiuents of the following type: halogen atoms, such as chlorine, bromine, fluorine; alkyl groups with 1 to 6 carbon atoms which may in turn be substituted by halogen, alkoxy, cyano or carboxyalkyl radicals; alkoxy radicals with 1 to 6 carbon atoms which may again be substituted by halogen, alkoxy, cyano or carboxyalkyl groups; esterified carboxy groups; sulphonic acid ester or sulphofiuoride groups; trifluoromethyl, acetyl, urethane, sulphonic acid amide, alkylsulphone, alkylthio or arylthio radicals. Examples of substituents of this kind are the methyl, ethyl, propyl, butyl, isobutyl, t-butyl or amyl groups; a methoxyor ethoxy-methyl group; a ,8-

methoxyor ethoxy-ethyl radical; a 'y-methoxyor ethoxy-propyl group; the methoxy, ethoxy, propoxy or butoxy radicals; a methoxy-, ethoxyor propoxy-methoxy or ethoxy group; the ethoxyor propoxy-carbonyl groups; the methoxyor ethoxy-carbonyl-methyl or -ethyl groups; the methoxyor ethoxy-carbonyl-methoxy or -ethoxy 10 radicals; a methoxyor et-hoxy-carbonylamino group; a N-phenylor N-phenyl-N-methyl-sulphonaniide radical; a methyl-sulphonyl or -sulphinyl group; a methyl-, ethylor phenyl-thio radical.

The dyestuffs which can be obtained by the present process are suitable, for example, as pigments for dyeing plastic masses and lacquers fast to migration. However, the dyestuffs or mixtures thereof serve primarily for dyeing natural fibres and synthetic materials, preferably polyamides, polyurethanes, polyacrylonitriles, polypropylene and polyesters; the polyesters, in particular, embrace linear aromatic polyesters, such as polyethylene terephthalate or polyesters from terephthalic acid and 1,4- bis-hydroxymethyl-cyclohexane, as well as cellulose esters, such as cellulose triacetate or cellulose ZVz-acetate. It is advantageous to bring the dye stuffs into a fine dispersion by the usual methods, for example, by reprecipitation, grinding or kneading in the presence of dispersing agents, and to apply them by known dyeing methods. Whereas cellulose 2 /2-acetate, for example, is dyed in the presence of Marseilles soap at 60-80 C., cellulose triacetate and polyamide fibres can be dyed at C. When dyeing polyethylene terephthalate fibres, the usual dyeing accelerators can be added or dyeing can be carried out at -145 C. under pressure. Dyeing or printing is preferably carried out according ot the thermosol process in which the printed or dyed fibre materials are heated, optionally after an intermediate drying, for a short time to temperatures in the range of about l80220 C. This heating is generally performed for periods of time of 30 seconds to 2 minutes.

The dyeings and prints obtained with the dyestufi's which can be produced according to the invention are characterised by a very good texture, a high dyestuffs yield and clear shades having excellent fastness to light, Washing, thermofixing and ironing.

In the following examples the parts are parts by weight, unless otherwise stated.

EXAMPLE 1 (a) 17.7 parts l-amino-anthraquinone and 6.5 parts dimethyl formamide in parts nitrobenzene are slowly mixed at 50-60 C. with 11 parts thionyl chloride, and the mixture is then stirred for 1 hour at 50-60 C. and subsequently stirred for about 1 hour in a vacuum at about 20-200 mm. Hg or nitrogen or air is passed through. The melt which contains pale yellow prisms is then mixed at 50-60 C. with 15 parts cyanoacetic acid morpholide, 20 parts of anhydrous sodium acetate are passed in and the mixture is then stirred at 50-60 C. until the formation of yellow small needles is completed. The product is filtered off with suction after cooling, washed with methanol and water, and after drying there are obtained 27.8 parts 13 (1 anthraquinonylamino)-a-cyanoacrylic acid morpholide=91% of theory.

Calculated for C H N O (387.3): N, 10.84%; 0, 16.54. Found: N, 10.80%; 0, 16.63.

(b) A fabric of polyethylene terephthalate fibres is impregnated on a foulard with a liquor containing, per litre, 20 g. B(l-anthraquinonylamino) a cyanoacrylic acid morpholide and 10 g. of a thermosol auxiliary, particularly a polyester as is described, for example, in Belgian patent specification No. 615,102. The fabric is then squeezed to a weight increase of 70% and dried in a suspended nozzle drier or drying carbinet at 80- 120 C. The fabric is subsequently treated in a stenter or nozzle hot flue with hot air at -220 C. for about 45 seconds, rinsed, reductively after-treated, if desired, then Washed, rinsed and dried. The reductive after-treatment in order to remove any dyestuffs particles superficially adhering to the fibres can be carried out by introducing the fabric at 25 C. into a liquor which contains 3-5 cc./ litre of a sodium hydroxide solution at 38 B and 1-2 g./litre of concentrated hydrosulphite, heating to 70 C. within about 15 minutes and keeping at 70 C. for a further minutes. The fabric is subsequently rinsed hot, acidified with 23 cc./litre of 85% formic acid at 50 C., rinsed and dried. There is obtained a golden yellow dyeing which is characterised by a high dyestufr yield and very good texture and by excellent fastness to light, thermofixing, washing, rubbing and sublimation. Similarly, a golden yellow dyeing is obtained when the polyethylene terephthalate fibres are replaced with polyester fibres from 1,4-bis-hydroxymethyl-cyclohexane and terephthalic acid or with cellulose triacetate or polyamide fibres.

(c) A previously cleaned and thermofixed fabric of polyethylene terephthalate fibres is printed with a printing paste which consists of the following component: 40 g. of the dyestutf mentioned in Example 1(b), 475 g. of

water, 1 part of Marseilles soap and 0.2 part B-(l-anthraquinonylamino -a-cyan0acrylic acid morpholide. A yellow dyeing of good fastness to light and washing is obtained.

EXAMPLE 2 water, 465 g. of crystal gum 1:2, and 20 g. of sulphonated- Calculated C23H19N303 castor oil. An alginate thickener may be used instead of Fellndi N, crystal gum. The printed and dried material is passed at When prlnt h y eceofdlhg to Example 190-220 C. over a high capacity stenter or through a the dyestlltf y e 0h fibres of p y y P condensation apparatus in order to fix the dyestuif. The thalate, Cellulose tflileetate 0f p ly Clear golden duration of the treatment is about 30-60 seconds. The yellow Shades h a haracterised by excellent fastfixed print so obtained is subsequently rinsed cold, soaped heSS t0 g Washlng, thefmefixlhg, h g and ewith 1-2 g./ litre of an anionactive detergent at 7080 C. Ahelogohs B h q hy h y y for about 10 minutes, rinsed first hot and then cold, and ae1d amlfles e Ph y 8 Instead of the y dried. There is obtained a print which corresponds to the fleetle ld p pendide mentloned above 1n the presentexdyeing of Example 1(b) and is characterized by the same p y e f aeld 21nude or the fohowthg amldes outstanding fastness properties. Similarly, a golden yellow 0f eyal'loaeetle' held! e y OF y the print is obtained when the polyethyleneterephthalate fibres y or dlethylamlde, 9 Y Y" are replaced with polyester fibres from 1,4-bis-hydroxy- Y- z-eyaneethylamlde, the 'hy Y h3 )1 methyl-cyclohexane and terephthalic acid or with cellulose Y YU- y y the t t t or l id fib acetoxyethyl)-amide, the his (2 methoxy-carbonyloxy- (d) 10 parts by weight polyethylene terephthalate fibres yD- the v y y mi are dyed at 125-130 c. for 2 hours in a bath which has the hy -y the 3-eth0XyprOPy1amde, been adjusted to pH 4.5 and consists of 400 parts by weight the Y $fP Py the y fy t of water and 0.1 part by weight of finely dispersed B-(lthe PY e thlomefphehde 0f Y -P P anthraquinonylamino) 0c cyanoacrylic acid morpholide, the y P Y the Y Q Y' they are subsequently rinsed and dried. There is obtained benzylarnld the fi-p nyl yl- 0r v-pheny propyl-amide, a golden yellow dye ng Which is characterized by very the anihde or N-rnethyl-amlrde, the 4-toluidide or N- good fastness properties. methyl-4-toluidide, the 4-chloroor 4-fluoro-anilide, the 4- (e) 10 parts by eight of polyethylene terephthalate anisidide OI N-methyl-4-anisidide, the 3-butoxyanilide, the fibres are dyed at 100 C. for 1 /2 hours in a bath which 4-eth0XymethY1-ahlhde, the P p Y- Y'P Y has been adjusted to pH 4.5 and consists of 400 parts by amlde, the -fiyyp y the Y' weight of water, 0.1 part by weight of finely dispersed 4-hydl'oxyethexyeafbohyl-phehylamide, the y- B-(l-anthraquinonylamino)-a-cyanoacrylic acid morphocarbonylmethyl-phenylamrde, the 4-ethoxycarbonylmethlide and 1.5 parts by weight o-cresotic acid methyl ester. oxy-phenylamide or the 4-pyridylamide. There is obtained a golden yellow dyeing which is char- In the following table there are stated the dyestuffs acterized by very good fastness properties. which are obtained from appropriately substituted N-(l- (f) 10 parts of polyamide fibres are dyed at the boil anthraquinonyl)-N'-dimethyl formarnidinium chlorides for 1 hour in a bath consisting of 400 parts of water, 0.2 according to Example 2, and their shades 0n polyester part of a conventional dispersing agent and 0.2 part of fibres:

Dyestuff Shade Example:

3 fl-(6-chl0ro-1-anthraquinonylamino)-a-cyanoacrylic acid Golden pyrrol' ide. ycllow. 4 B-(SJ-dichlor0-1-anthraquinonylamino)-0z-cyanoacrylic D0.

acid ethylamide. 5 ,8-(6-flu0ro-l-anthraquinonylamino)-a-cyanoacrylic acid- D0.

2-methoxyethylamidc. 6 B-(6,7-difluoro-lanthraquinonylarnino)-oz-cyanoacrylic Do.

acid-bis-(fimiethoxycthyl)amide. 7 B-(fi-mcthylthio-l-anthraquinonylamino)-a-cyanoacrylic Do.

acid benzylamide. 8 fl-(Gphcnylthio-l-anthraquinonylamino)-a-cyanoacrylic Do.

acid-3-bromoanilide. 9 fl-(6-1nethylsulphonyl-lanthraquinonylamino)-a-cyano- Do.

acrylic acid-2,5-dimethoxyanilidc. 10 13-(G-phenylsulphonyl-l-anthraquinonylarnino)-0z-cyano- Do.

acrylic acid-N-mcthylanilide. ll B-(4(2-hydroxyethylthio)-l-anthraquinonylamino)- Orange.

a-cyanoacrylic acid morpholidc. 12 fl-(4-phenylthiodanfihraquinonylamin0)-c-cyanoacrylic Do.

acid morpholide.

finely dispersed B (1 anthraquinonylarnino)-a-cyan0- EXAMPLE 13 acrylic acid rnorpholide. There is obtained a clear yellow 19 parts 4 hydroxy-l-arnino-anthraquinone and 6.3

dyeing of very good fastness properties. Instead of polyamide fibres, polyurethanc fibres can be used with equally good results.

(g) 20 parts of cellulose 2 /z-acetate fibres are dyed at parts dimethyl formamide in 150 parts o-dichlorobenzene are mixed at 5060 C. with 10.5 parts thionyl chloride, and when the formation of the amidinium chloride in the form of yellow-red prisms is completed, the mixture is C. for one hour in a bath consisting of 600 parts of 75 stirred in a vacuum for about 1 hour. 15.5 parts cyanoacetic acid morpholide and 20 parts of anhydrous sodium acetate are then added, and the mixture is stirred at 50- 70 C. until the formation of the dye-stuff is completed. After cooling, the product which crystallises in the form of red prisms is filtered off with suction, washed with methanol and water, and there are obtained 30.8 parts p-(4-hydroxy-l-anthraquinonylamino) a cyanoacrylic acid morpholide=92% of theory.

Calculated for C H N O (403.3): N, 10.42%; 0, 19.82%. Found: N, 10.31%; 0, 19.89%.

When printed on fibres of polyethyleneterephthalate, cellulose triacetate or polyamide according to Example 1(b) or 1(c), the dyestuif yields, with high dyestuflf yields and very good texture, brilliant red shades which are characterised by excellent fastness to light, washing, thermofixing, rubbing and ironing.

Analogous [3-(4-hydroxy 1 anthraquinonylamino)-acyanoacrylic acid amides are obtained by using, instead of the cyanoacetic acid morpholide mentioned in the present example, cyanoacetic acid amide or the following amides of cyanoacetic acid: the methylor isopropylamide, the methyl-ethylor diethyl-amide, the cyclohexylor 4-hydroxycyclohexyl-amide, the 2-chloro-, 2-hydroxy-, 2-methoxyor 2-cyano-ethylamide, the bias-(Z-hydroxyethyl)-, bis (2 ethoxy-ethyl)- or bis (2-cyanoethyl)- amide, the acetoxyethylamide or bis-(acetoxyethyl)- amide, the bis-(methoxycarbonyloxethyl)-amide, the ethyl-(2-cyanoethyl)-amide, the 4- methoxybutyla-mide, the \a-hydroxyor w-methoxy-fl-ethoxyethylamide, the pyrrolidide, piperidide, thiomorpholide or N-ethylpiperazide, the 3-methylbenzylamide, the anilide, N-methylanilide, 4 ethoxyanilide, 3 methoxy-carbonbylaminophenylamide or 4-methylthioanilide.

EXAMPLE 14 40.4 parts 1-amino-4-methoxy-anthraquinone in 250 parts nitrobenzene are converted into the amidinium chloride with 12.6 parts dimethyl formamide and 21 parts thionyl chloride according to Example 1(a). The melt is mixed with 27 parts cyanoacetic acid pyrrolidide and 40 parts of anhydrous sodium acetate and the mixture is stirred at 5070 C. until the formation of the dyestufi is completed, the product which crystallises in the form of orange-coloured prisms is filtered off with suction after cooling, washed with methanol and water, and the are obtained 57 parts [3-(4 methoxy-1-anthraquinonylamino) ot-cyanoacrylic acid pyrrolidide=89'% of theory.

Calculated for C H N O (401.4): N, 10.48%; 0, 15.97%. Found: N, 10.42%; 0, 16.11%.

When dyed or printed according to Example 1(b) or 1(c), the dyestuif yields on fibres of polyethylene terephthalate, cellulose triacetate and polyamide orange shades of excellent fastness to light, washing, thermofixing, rubbing and ironing. Analogous ,8-(4-methoxy-1- anthraquinonylamino)-a-cyanoacrylic acid amides are obtained by using, instead of the cyanoacetic acid pyrrolidide mentioned in the present example, cyanoacetic acid amide or the following amides of cyanoacetic acid: the dimethylamide, n-amylamide, fl-propoxyethylamide or ,B-cyanoethylamide, the bis-(2-hydroxyethyl)- or -(2- cyanoethyl)-amide, the bis-(fl-acetoxyethyD-amide, the ([l-cyanoethyl)-(/3-acetoxyethyl) amide, the ethoxycarbonylmethylor S-methoxycarbonylmethyl-amide, the 4- methylcyclohexylamide, the morpholide, thiomorpholide or piperidide, the allylamide or li-phenylethylamide, the 3-cyano-benzyl- 0r bis-(benzyl)- or bis-(benzyl)-amide, the anilide, N-methylanilide, 3-butoxyanilide, 4-phenylthiophenylamide or 3-pyridylamide. Analogous 13-(4- alkoxy 1 anthraquinonylamino) a-cyanoacrylic acid amides are also obtained by using for the condensation with cyanoacetic acid amides the 4-ethoxy-, 4-propoxyor 4-benzyloxy-l-amino-anthraquinones, instead of the 4-methoxy-l-aminoanthraquinone mentioned in the present example.

14 EXAMPLE 15 19 parts 1-amino-5-hydroxy-anthraquinone in parts nitrobenzene are converted into the amidinium chloride with 6.3 parts dimethyl formamide and 10.5 parts thionyl chloride according to Example 1(a). The melt is mixed with 18.5 parts cyanoacetic acid-bis-(ot-cyanoethyD- amide and 17 parts of anhydrous sodium acetate, the mixture is stirred at 50-70 C. until the formation of the dyestulf is completed, the product which crystallises in the form of yellow small needles is filtered off with suction, washed with methanol and water, and there are obtained 31 parts fl-(S-hydroxy-1-anthraquinonylamino)- a-cyanoacrylic acid-bis-(B-cyanoethyl)-amide=92% of theory.

Calculated for C I-1 N 0 (423.4): N. 16.53%; 0, 11.32%. Found: N, 16.67%; 0, 11.26%.

When dyed or printed according to Example 1(b) or 1(c), the dyestuif yields on fibres of polyethylene terephthalate, cellulose triacetate and polyamide golden yellow shades of very good fastness to light, thermofixing and washing. Analogous ,9-(5-hydroxy-l-anthraquinonylamino)-a-cyanoacetic acid amides are obtained by using, instead of the cyanoacetic acid-bis-(B-cyanoethyl)-amide mentioned above in the present Example, cyanoacetic acid amide or the following amides of cyanoacetic acid: the n-propylamide, dipropylamide, bis-(B-ethoxyethyl)-amide, bis-(fl-acetoxyethyl-amide, the w-ethoxy-fi-ethoxy-ethylamide, the pyrrolidide, morpholide or thio morpholide, the anilide of N-methylanilide.

EXAMPLE 16 28.8 parts N (4,8-dihydroxy-5-amino-l-anthraquinonyl)-N-dimethyl formamidinium chloride and 13.6 parts cyanoacetic acid diethylamide in parts nitrobenzene are mixed at 50-60 C. with 14 parts of anhydrous sodium acetate, and the mixture is stirred until the formation of the dyestuff is completed. After cooling, the product which crystallises in the form of reddish blue small needles is filtered off with suction, washed with methanol and water, and there are obtained 31 parts 13-(4,8-dihydroxy-5-amino-l-anthraquinonylamino) 04 cyanoacrylic acid diethylamide=93% of theory.

Calculated for C H N O (420.4): N, 13.33%, 0, 19.07%. Found: N, 13.26%; 0, 10.01%.

When dyed or printed on to fibres of polyethylene terephthalate, cellulose triacetate or polyamide according to Example 1(b) or 1(c), the dyestuif yields deep reddish blue shades of excellent fastness to light, washing thermofixing and ironing.

Analogous B- (4, S-dihydroxy-S-amino- 1 -anthraquinonylamino)-a-cyanoacrylic acid amides are obtained by using for the conversion of N-(4,8-dihydroxy-5-amino-1- anthraquinonyl)-N-dimethyl formamidinium chloride, instead of cyanoacetic diethylamide, cyanoacetic acid amide or the following amides of cyanoacetic acid: the n-hexylamide, di-n-butylamide, bis-(B-n-propoxy-ethyD- or -('y-hydroxypropyl)-amide, the bis(4-meth0xy-butyl)- or -(w-methoxy-B-ethoxyethyl)-amide, the 4-ethoxybenxylamide, y-phenylpropylamide, the morpholide or piperidide, the N-ethylanilide, the 3-bromo-anilide, the 3,4- methylenedioxy-phenylamide, the N-methyl-4-propoxyphenylamide, the 4-propoxymethoxy-phenylamide, the 4 ethoxycarbonylphenylamide or 3 methylsulphonylphenylamide.

Brominated or chlorinated B-(4,8-dihydroxy-5-amino- 1 anthraquinonylamino) a cyanoacrylic acid amides which dye in reddish blue shades are also obtained, when brominated or chlorinated N-(4,8-dihydroxy-5-amino-1- anthraquinonyl)-N-dimethyl formamidinium chlorides which are obtainable from 1,5 diamino-4,8-dihydroxyanthraquinones containing 5 to 25% bromine or chlorine and prepared by bromination or chlorination of 1,5- diamino-4,8-dihydroxy-anthraquinones in solvents such as o-dichlorobenzene or sulphuric acid, are reacted according to Example 16 with the stated cyanoacetic acid amides.

EXAMPLE 17 28.8 parts N-(4,5-dihydroxy-8 amino 1 anthraquinonyl)-N-dimethyl formamidinium chloride and 17.6 parts cyanoacetic acid-bis-(B-hydroxyethyD-amide are condensed in 180 parts nitrobenzene according to Example 16 at 5060 C. in the presence of 14 parts of anhydrous sodium acetate. There are obtained 34.6 parts=96% of theory, of fi-(4,5-dihydroxy-8-amino-1- anthraquinonylamino)-a cyanoacrylic acid bis Q-hydroxyethyl)-amide which crystallises in the form of reddish blue needles.

Calculated for C22H20N407 (452.4): N, 12.41%; 0,

1 6 EXAMPLE 1:;

37.6 parts N- (4,8-dihydroxy-5-amino-6-phenylthio-1- anthraquinonyl)-N-dimethyl formamidinium chloride and parts cyanoacetic acid morpholide in 240 parts nitrobenzene are mixed at 7080 C. with 14 parts of anhydrous sodium acetate and the mixture is stirred until the formation of the dyestutf is completed. After cooling, the product which crystallises in the form of reddish blue small needles is'filtered off with suction, washed with methanol and water, and there are obtained 41 parts ,8 (4, 8 dihydroxy-5-amino-6-phenylthio-1-anthraquinonyl-a-cyanoacrylic acid morpohlide=94.5% of theory.

Calculated for C H N O S (542.4): N, 10.32%; 0, 17.70%. Found: N, 10.21%; 0, 17.78%.

24.82%. Found: N, 12.32%; 0, 24.96%. 15 When dyed or printed according to Example 1(b) or When dyed or printed on to fibres of polyethylene 1(0), the dyestuff yields on fibres of polyethylene terephterephthalate cellulose triacetate or polyamide, the dyethalate, cellulose triacetate or polyamide, reddish blue stuff yields navy-blue shades of excellent fastness to light, shades which exhibit very good fastness to light, washing washing, thermofixing and ironing. and thermofixing.

Analogous B-(4,S-dihydroxy-S-amino-l-anthraqinonyl- In the following table there are stated the dyestuffs amino)-a-cyanoacrylic acid amides are obtained by using which are obtained from appropriately substituted N-(4,8- for the conversion of N-(4,5-dihydroxy-8-amino-l-anthradihydroxy-S-amino-l-anthraquinonyl)-N'-dimethyl formquinonyl)-N'-dimethyl formamidinium chloride, instead amidinium chlorides according to Example 18, and their 0f cyanoacetic acid-bis-(,B-hydroxyethyl)-amide, cyanoshades on polyethylene terephthalate fibres.

Dycstufi Shade Example:

19 fl-(4,8-dihydroxy-5-amino-6-methylthio1-anthraquinonyl- Reddish amino)-a-cyanoacrylic acid-3-phenylpropylamide. blue. 20 B-(4,8-dihydroxy-5-amino-fi-phenylsulphonyl-1- D0.

anthraquinonylamino)-a-cyan0aery1ic acid-2- methoxyethylamide. 21 B-(4,8-dihydroxy-5-amino-fi-methylsulphonyl-l- D0.

anthraquinonylamino)-a-cyan0acrylic acid dirnethylamide. 22 6-(4,8-dihydroxy 5-amino-6-br0mo-1-anthraquinonyl- Do.

amino) -a-cyanoacrylic acid piperidide. 23 13-(4,8-dihydroxy-5-amin0-7-bromo-l-anthraquinonyl- D0.

amino)-a-cyanoacrylic acid pyrrolidide.

acetic acid amide or the following amides of cyanoacetic EXAMPLE 24 acid: the t-butylamide, the ,B-methoxycarbonyl ethyl- 32.6 parts N-(4,S-dihydroxy-8-amino-7-methylthio-1- amide, the ethyl-(2-cyanoethyl)-amide, the cyclohexyanthraquinonyl)N-dimethyl formamidinium chloride in amide, the pyrrolidide, piperidide, morpholide or thiomor- 180 parts nitrobenzene are condensed according to Expholide, the bis-(fi-allyD-amide, the anilide, 4-,3-ethoxyample 18 with 14.7 parts cyanoacetic acid piperidide in ethyl-anilide, the 3 5 ethoxyethoxy-anilide, 3-sulphonthe presence of 14 parts of anhydrous sodium acetate. amido phenylamide or 4 ,6- methoxyethoxycarbonyl- There are obtained 35 parts ,8-(4,5-dihydroxy-8-amino-7- phenylamide. methylthio-l-anthraquinonylaminoh; cyanoacrylic acid Brominated or chlorinated B-(4,5-dihydroxy-8-aminopiperidide=91.4% of theory.

1 anthraquinonylamino) acyanoacrylic acid amides Calculated for C H N O S (478.4): N, 11.70%; 0, which dye in deep navy-blue shades are also obtained, 16.72%. Found: N, 11.58%; 0, 16.84%.

when the brominated or chlorinated N-(4,5-dihydroxy-8- When dyed or printed according to Example 1(b) or amino-l-anthraquinonyl) N dimethyl formamidinium 1(0), the dyestuff yields on fibres of polyethylene terephchlorides which can be obtained from 4,5-dihydroxy-1,8- thalate, cellulose triacetate or polyamide navy-blue shades diamino-anthraquinones containing 525% bromine or of very good fastness to light, washing and thermofixing. chlorine and prepared by bromination or chlorination of In the following table there are stated the dyestuffs 4,5-dihydroxy-1,8-diamino-anthraquinone in solvents which are obtained from appropriately substituted N- such as o-dichlorobenzene or sulphuric acid, are reacted according to Example 17 with the stated cyanoacetic acid amides.

(4,5-dihydroxy 8 amino-l-anthraquinonyl)-Ndimethyl formamidinium chlorides according to Example 24, and their shades on polyethylene terephthalate fibres.

Dyestufi Shade Example:

25 B-(4,5-dihydroxy-8-amino-7-phenylthio-l-anthraqulnonylamino)-a-eyan0- N avy-blue.

acrylic acid-2-chloroethy1aminde.

26 fl-(4,5-dihydroxy-8-amino-7-methylsulphonyl-1-anthraquinonylammo)41- Do.

cyanoacrylic acid-bis-(2-hydroxyethy1)-amide.

27 fi-(4,5-dihydroxy-8-amino-7-phenylsulphonyl-l-anthraquinonylamino)-a- Do.

cyanoacrylic acid-bis-(2-hydroxyethyl)-amide.

28 6-(4,5-dihydroxy-S-amino-7-bromo-l-anthraquinonylamino)-a-cyano- Do.

acrylic acid benzyl-amide.

29 B-(4,5-dihydroxy-S-amino-dbromo-l-anthraquinonylamino)-a-cyanoacrylic D0.

acid diethyl-amide.

1 7 EXAMPLE 30 32.2 parts N-(4-phenylamino-1-anthraquinonyl-N-dimethyl formamidinium chloride and 19.4 parts cyanoacetic acid-bis-(fl-methoxyethyl)-amide in 150 parts nitrobenzene are mixed at 50-60 C. with 10 g. of anhydrous sodium acetate and the mixture is stirred at 5060 g. until the formation of the dyestulf in the shape of bluetriactate or polyamide, the dyestulf yields grey-blue shades of excellent fastness to washing and thermofixing.

In the following table there are stated the dyestuffs which are obtained from appropriately 4-substituted 1- amino-4-aryl, -aralkyl-, -cycloalkylor -alkyl-amino-anthraquinones according to Example 31, and their shades on polyethylene terephthalate fibres:

Dyestufi Shade Example:

32 B-(4-p-ch1or0phenylammo-l-antln'aquuionyl-amnio)-a-cyanoacrylic acid Greyblue.

molp e.

33 fl-(4-p-mcthylp11enylamino-l-anthraquinonyl-amino)-a-cyanoaerylic acid Do.

diethylamide.

34 fl-(Haegzylamino-1-anthraquinonylamino-mcyanoacrylie acid4-meth0xy- Greyisli blue.

35 13-(4cyclohexylamino1-anthraquinonyl-amino)-a-eyauoacrylic acid-3-t1'i- Do.

fluoro-methylamlide.

36 B-(4methylammo-l-anthraquinonylamino)-a-eyanoaerylic acid anilidc Do.

37 B-(4 m-b 9n0phenylam1no-l-anthraquinonyl-amino)-a cyauacrylic acid Blue-grey.

piperl r e.

38 13(4-2,4,6-trimethylphenylamino-l-anthraquinonylamino)-a-cyano-acryl- Grcyish blue.

ie acid-ethyI-Z-cyanOethyl-amide.

39 9 (4 m-cyanophenylamm0-l-anthraquinonyl-amino)-a-cyan0acrylic acid Blue-grey.

dlmethylamide.

grey prisms is completed. The product is filtered off with suction after cooling, and after washing with methanol and water there are obtained 39 parts ,8-(4-phenylaminol-anthraquinonylamino)-a-cyanoacrylic acid-bis-(Z-methoxyethyl)-amide=93.5% of theory.

Calculated for C H N O (524.5): N, 10.68%; 0, 15.25%. Found: N, 10.64%; 0, 15.31%.

When dyed or printed according to Example 1(b) or 1(0) onto polyester fibres of polyethylene terephthalate or of 1,4-bis-hydroxymethyl-cyclohexane and terephthalate acid, or onto fibres of cellulose triacetate or polyamide, the dyestuff yields blue-grey shades of excellent fastness properties.

Analogous 8-(4-phenylamino-l-anthraquinonylamino tat-cyanoacrylic acid esters are obtained by using for the conversion of N-(4-phenylamino-l-anthraquinonyl)-N' dimethyl formamidinium chloride, instead of cyanoacetic acid-bis-(B-methoxyethyD-amide, cyanoacetic acid amide or the following amides of cyanoacetic acid: the methylamide, diethylamide, 4-hydroxy-cyclohexylamide, 2-acetoxyethylamide; the bis-(2-cyanoethyl)- or -(2-hydroxyethyl)-amide; the bis-(2'-acetoxyethyl)- or -(2-methoxycarbonyloxy-ethyl)-amide; the ethyl (2 cyanoethyl)- amide; the bis-(w-methoxy-fl-ethoxyethyl)-amide; the pyrrolidide, piperidide, morpholide, thiomorpholide, N'- methylpiperazide; the 4-chlorobenzylamide; the bis-(2- allyl)-amide, the anilide, N-methyl-anilide, 4-chloroanilide, 3-trifluoromethylanilide, 3-ethoxy-anilide, 4-methoxymethyl-anilide, 4-[3-hydroxyethoxy-phenylamide; the 3- ethoxycarbonyl-phenylamide; the 4-methoxycarbonylmethoxy-phenylamide or the 4-pyridylamide.

EXAMPLE 31 27.4 parts 1-amino-4-(p-methoxyphenylamino)-anthraquinone and 6.3 parts dimethyl formamide in 150 parts nitrobenzene are mixed at 5060 C. with 10.5 parts thionyl chloride, and when the formation of the amidinium chloride is completed, the mixture is stirred in a vacuum for about 1 hour. parts cyanoacetic acid-bis-(Z-acetoxyethyl)-amide are then added, 20 parts anhydrous sodium acetate are introduced and the mixture is stirred at 5060 C. until the formation of the dyestuff in the shape of darkblue small needles is completed. The product is filtered off with suction when cold, washed with methanol and water and there are obtained 42 parts 3-(4-p-methoxyphenylamino-1-anthraquinonylamino) tat-cyanoacrylic acid-bis- (2-acetoxyethyl)-amide=91% of theory.

Calculated for C32H23N4O7 N, O, 19.33%. Found: N, 9.58%; O, 19.41%.

When dyed or printed according to Example 1(b) or 1(c) on to fibres of polyethylene terephthalate, cellulose EXAMPLE 40 21.6 parts 4,5,8-trihydr0xy-l-amino-anthraquinone and 6.3 parts dimethyl formamide in parts o-dichlorobenzene are mixed at 5060C. with 10.5 parts thionyl chloride, and when the formation of the amidinium chloride is completed, the mixture is stirred in a vacuum for about 1 hour. 15 parts cyanoacetic acid morpholide and 20 parts of anhydrous sodium acetate are then added and the mixture is stirred at 5060 C. until the formation of the dyestuff is completed. The product which crystallises in the form of orange-coloured prisms is filtered off with suction after cooling, washed with methanol and water, and there are obtained 31.6 parts fi-(4,5,8-trihydroxy-1- anthraquinonylamino)-u-cyanoacrylic acid morpholide: 91% of theory.

Calculated for C22H17N3O7 (435.3): N, 9.66%; O, 25.73%. Found: N, 9.53%; O, 25.69%.

When dyed or printed according to Example 1(b) or 1(0), the dyestuff yields on fibres of polyethyleneterephthalate, cellulose triacetate or polyamide yellowish red shades of very good fastness to thermofixing, light and washing.

Analogous B-(4,5,8 trihydroxy 1 anthraquinonylamino)-a-cyanoacrylic acid amides are obtained by using, instead of the cyanoacetic acid morpholide mentioned above in the present Example, cyanoacetic acid amide or the following amides of cyanoacetic acid: the diethylamide, Z-methoxyethylamide, bis-(B-cyanoethyD-amide, benzylamide, piperidide or thiomorpholide, the anilide, N-methylanilide, 4-methoxyanilide, N-methyl-4-methoxyanilide or the 4-fihydroxyethoxycarbonyl-phenylamide.

EXAMPLE 41 23.9 parts 5-nitro-4,8-dihydroxy-l-amino-anthraquinone in parts o-dichlorobenzene are converted with 6.3 parts dimethyl formamide and 10.5 parts thionyl chloride into the amidinium chloride according to Example 40. 15 parts cyanoacetic acid morpholide and 12 parts of anhydrous sodium acetate are added, and the mixture is stirred at 5070 C. until the formation of the dyestulf in the shape of red prisms is completed. The product is filtered oil with suction after cooling, washed with methanol and water, and there are obtained 35.9 parts fl-(5-nitro-4,8-dihydroxy-l-anthraquinonylamino) a cyanoacrylic acid morpholide=97% of theory.

Calculated for C I-1 N 0 (464.3): N, 12.05%; 0, 27.58%. Found: N, 12.13%; 0, 27.64%.

When dyed or printed according to Example 1(b) or 1(c), the dyestutf yields on fibres of polyethylene terephthalate, cellulose triacetate or polyamide bluish red shades of excellent fastness to light, washing and thermofixing. Analogous ,8-(-nitro-4,8-dihydroxy-l-anthraquinonylamino)-a-cyanoacrylic acid amides are obtained by using, instead of the cyanoacetic acid morpholide mentioned in the present example, cyanoacetic acid amide or the following amides of cyanoacetic acid: the dimethylamide, 2-cyanoethylamide, ethoxycarbonylmethylamide; the bis-,(2-methoxyethyl)- or -(2-acetoxyethyl)- amide; the fl-allylamide; the piperidide or pyrrolidide; the anilide, 3-ethoxyanilide, 3-fluoro-anilide or 4-ethoxycarbonylmethoxy-phenylamide.

Analogously, ,8-(8-nitro-4,5-dihydroxy-1-anthraquinonylamino)-a-cyanocrylic acid amides which dye polyester and polyamide fibres in red shades are obtained by using, instead of the 5-nitro-4,S-dihydroxy-l-arnino-anthraquinone, the isomeric 8-nitro-4,5-dihydroxy-l-amino-anthraquinone.

EXAMPLE 42 22.2 parts 1-amino-5-acetylamino-anthraquinone are converted with 6.3 parts dimethyl formamide and 10.5 parts thionyl chloride in 150 parts nitrobenzene at 50 60 C. into the amidinium chloride, and parts cyanoacetic acid morpholide and parts of anhydrous sodium acetate are then added. The mixture is stirred at 50-60 C. until the formation of the dyestuif is completed, the product which crystallises in the form of yellow small needles is filtered off with suction after cooling, washed with methanol and water, and there are obtained 32 parts 5 (S-acetylamino-l-anthraquinonyla mino) -a-cyanocrylic acid morpholide:91% of theory.

Calculated for C H N O (444.4): N, 12.61%; 0, 17.98%. Found: N, 12.57%; 0, 18.08%.

When dyed or printed according to Example 1(b) or 1(c), the dyestuff yields on fibers of polyethylene terephthalate, cellulose triacetate or polyamide clear goldenyellow shades of excellent fastness to light, washing, thermo-fixing and rubbing. Analogous ,B-(S-acetylaminol-anthraquinonylamino)-o-cyanoacrylic acid amides are obtained by using, instead of the cyanoacetic acid morpholide mentioned in the present example, cyanoacetic acid amide or the following amides of cyanoacetic acid: the n propylamide, 2-hydroxyethylamide, di-(n-propyl)- amide; the bis-(2-fluoroethyl)- or-,(2-hydroxyethyl)- amide; the bis (2 -methoxyethyl)- or -(2-methoxycarbonyloxyethyl)-amide; the 3-methoxy-propylamide; the piperidide, pyrrolidide or thiomorpholide; the benzylamide; the anilide, N-methyl-anilide, 4-methyl-analide, 3-butoxy-anilide or the 4-fl-methoxyethoxycarbonyl-phenylamide.

EXAMPLE 43 15 parts 1,S-diamino-anthraquinone are converted with 10.5 parts dimethyl formamide and 16.8 parts thionyl chloride in 150 parts nitrobenzene at 50-60 C. into the bis-amidinium chloride; 24.2 parts cyanoacetic acid anilide and parts of anhydrous sodium acetate are added and the mixture is stirred at 50-60 C. until the formation of the dyestuff is completed. After cooling, the product which crystallises in the form of yellow-orange small needles is filtered off with suction, washed with methanol and water, and there are obtained 35.5 parts 1,5-bis-(2- phenyl-aminocarbonyl 2' cyanoethyleneamino)-anthraquinone=98% of theory.

Calculated for C34H22NO5 N, O, 11.7%. Found: N, 14.34%; 0, 11.93%.

In lacquers of synthetic resin the dyestuif is suitable as a golden-yellow pigment which is fast to light and solvents.

EXAMPLE 44 20 parts 1,4-diamino-anthraquinone are converted with 14 parts dimethyl formamide and 23.6 parts thionyl chloride in 210 parts nitrobenzene at 5060 C. into the bis-amidinium chloride; 30 parts cyanoacetic acid-B- methoxyethylamide and parts of anhydrous sodium acetate are added, and the mixture is stirred at 50-60 C. until the formation of the dyestuff is completed. The

product which crystallises in the form of brown-red needles is filtered off with suction after cooling, washed with methanol and water, and there are obtained 43.5 parts 1,4-bis-(2-fl-methoxyethylamido-carbonyl-2'-cyanoethylene-amino)-anthraquinone=95.5% of theory.

Calculated for C H N O (542.5): N, 15.49%; 0, 17.70%. Found: N, 15.31%; 0, 17.89%.

When dyed or printed according to Example 1(b) or 1(c), the dyestulf yields on fibres of polyethylene terephthalate or cellulose triacetate brownish red shades of very good fastness to light, Washing and thermofixing. When the dyestuif is incorporated as a pigment with lacquers of synthetic resin, a brownish red coloration is obtained, which is fast to light and solvents.

EXAMPLE 45 22.7 parts 4,8-diamino-1,S-dihydroxy-anthraquinone are converted with 14 parts dimethyl formamide and 23.6 parts thionyl chloride in 210 parts nitrobenzene at 50- 60 C. into the bis-amidinium chloride Which crystallises in the form of pale violet prisms; 28.4 parts cyanoacetic acid-B-methoxyethylaanide and 40 parts sodium acetate are added and the mixture is stirred at -110 C. until the formation of the dycstufi' in the shape of blue-violet small needles is completed. The product is filtered off with suction after cooling, washed with methanol and water, and there are obtained 46 parts 4,8-bis-(2'-B- methoxy ethylaminocarbonyl-2'-cyanoethylene-amino)- 1,S-dihydroxy-anthraquinone:% of theory.

Calculated for C H N O (574.5): N, 14.64; 0, 22.30%. Found: N, 14.43%; 0, 22.48%.

When dyed or printed according to Example 1(b) or 1(c), the dyestutf yields on fibres of polyethylene terephthalate or cellulose triacetate red-blue shades of excellent fastness to light, washing and sublimation. If, instead of 4,8-diamino-1,5-dihydroxy-anthraquinone, the isomeric 4,5-diamino-1,8-dihydroxy-anthraquinone is used, then there is obtained 4,5-bis-(2' 6-methoxy-ethylamino-carbony1-2'-cyanoethyleneamino) 1,8 dihydroxy anthraquinone which dyes polyester fibres in red-blue shades.

EXAMPLE 46 22.6 parts 1,4,5,8-tetraamino-anthraquinone are converted with 27 parts dimethyl formamide and 44 parts thionyl chloride in 320 .parts nitrobenzene at 70-80 C. into the tetrakis-amidinium chloride; 45 parts cyanoacetic acid dimethylamide and 75 parts of anhydrous sodium acetate are added, and the mixture is stirred at 120 C. until the formation of the dyestutf is completed. The product is filtered off with suction after cooling, washed with methanol and water, and there are obtained 61.6 parts 1,4,5,8-tetrakis-(2-dimethylamidocarbonyl 2'-cyanoethylene-amino -anthraquinone=97% of theory.

Calculatedfor C H N O (756.6): N, 22.2%; 0, 12.68%. Found: N, 21.84%; 0, 13.05%.

The dyestuff can be used as a red-blue pigment which is fast to light and solvents for the coloration of synthetic materials.

EXAMPLE 47 25 parts N-(2-anthraquinonyl)-N-dimethyl formami dinium chloride and 15 parts cyanoacetic acid morpholide are stirred with 20 parts of anhydrous sodium acetate in parts nitrobenzene at 50-60 C. until the formation of the dyestutf in the form of greenish yellow small needles is completed. The product is filtered off with suction after cooling, washed with methanol and water, and there are obtained 26.8 parts B-(Z-anthraquinonylamino)-a-cyanoacrylic acid morpholide=91.5% of theory.

Calculated for C H N O (387.3): N, 10.84%; 0, 16.54%. Found: N, 10.87%; 0, 16.50%.

The same dyestutf is obtained in an analogous manner by using, instead of N-(2-anthraquinonyl)-N'-dimethyl formamidinium chloride, the N-(2-anthraquinonyl)-N- gen, alkoxy of l-6 carbon atoms, cyano, and carboxyalkyl of l-6 carbon atoms in the alkyl group, esterified carboxy, sulfonic acid ester, sulfofluoride, trifluoromethyl, acetyl, urethane, sulfonic acid amide, alkylsulfone of 16 carbon atoms in the alkyl group, and phenylthio; and R and R may be an alkylene of l-6 methylene groups combined with the N in the above formula and -2 additional hetero atoms selected from the group consisting of O, N and S to form a heterocycle selected from the group consisting of pyrrolyl, imidazolyl, imidazolinyl, pyrazolyl, pyrazolinyl, pyrazolidinyl, oxazolinyl, thiazolinyl, oxadiazolyl, triazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, piperidinyl,

Dyestufi Shade Example:

48 B(4-hydroxy-2-bromo-1-anthraqu1n0nylam1no)-a-eyanoacrylic acid di- Yellowish red.

methylamide. 49 B-(4-hyd1oxy-3-bromo-l-anthraqulnonylamino)-a-cyanoaerylie aeid-2'- Red.

cyanoethylamide. 50 6-(4-methoXy-2-hrom01-anthraquinonylamino)-a-cyanoacrylie acid-2 Orange,

ethoxyethylamide. I 51 6-tg ritroi-amino-l-anthraqu1n0nylamino) a-eyanoacrylie acid pyrrol- Navy-blue.-

1 l 8. 52 fl-(B-methoxy-Lamino-l-anthraquinonylamino)-a-eyanoacrylic aeid-bis- B1uevio1et.

(B-methoxyethyD-amide. 53 B (3-phen0xy-4-amin0 1-authraquinonylamino)-a-eyanoaerylie aeid di- Do.

ethylamide. A 54 B-(3-brom0A-amino-l-anthraquin0nylam1no)-a-eyan0acrylic acid-bis-(B- Do.

hydroxyethyD-amide. 55 B-(3-cyano-4-amino-1-anthraquinonylammo)-a-eyanoaerylic acid n- D0.

butylamide. B- (341 39,tyl+amino-1-anthraquinonylarnino)-a-eya.noaerylic acid benzyl Do.

9.1111 8. 57 6-(3-ethoxycarbonyl-4-amind1-anthraquinonylamino)-a-cyanoacrylic Do.

acid molpholide. 58 B-(3-(2hydroxyethylthio)-4-amino-l-anthraquinonylnmino)-a-cyano- Reddish blue.

acrylic acid dimethylamide. 59 B-(3-methylsulph0nyl-4-amino-l-anthraquinonylarnino)-a-cyanoaerylie Bluish red.

acid-2-hydroxyethyl-amide. 60 fl-(3-phenylsulphonyl-4-amino-1-anthraquinonylamlno)-a-cyanoacrylic Do.

acid methylamide. 61 fl-t ipropionylamino-l-anthraquinonylamino)-a-cyanoaery1ie acid am- Red.

1 e. B-(2-brom0-4-1)-toluenesulphonylamino-l-anthraqulnonylamino)-a- Yellowish red.

cyanoacrylie acid-w-hydroxyethoxyethyl-nmide. 63 B-(5,8-dichlor0-4-amin0-l-anthraquinonylamino)-a-eyanoacrylie acid-4- Blue violet.

methoxyanilide. 64 1,4bis(2-ethylamidoearbonyl-2-cyanoethyleneamino)-5,8-dil1ydroxy- Bluish red.

anthraquinone. 65 5-(2-pyrrolidinoca1'bonyl-2-cyano-ethyleneamino)-l,9-thiazole-anthrone. Yellow. 66 5-(2-rn0rpholinoearbonyl-2-cyano-ethyleneamino)-1,9-pyrazole- Do.

anthrone. 67 5-(2-thiomorpho1inocarbonyl-2-cyanoethylene-amino)-1,9-anthra- Do.

pyrimidine. 68 4-(2-bis-(B-acetoxyethyl)-aminocarbonyl-2-eyano-ethylene-amino)-1- Orange.

methyl-l,Q-anthrapyridone.

What I claim is: 1. An anthraquinone dyestuff of the formula wherein A is an anthraquinone radical, n is an integer from 1 to 4, and R and R are selected from the group consisting of hydrogen; lower alkyl of 1-6 carbon atoms; lower alkyl of 1-6 carbon atoms substituted with one or more members from the group consisting of hydroxy, hy-droxy acylated by an aliphatic carboxylic acid, hydroxy acylated by a carbonic acid semiester, alkoxy, hydroxyalkyleneoxy, alkoxyalkyleneoxy, alkoxycarbonyl, or cyano, wherein alkoxy and alkylene each contain 1-6 carbon atoms; cyclopentyl; cyclohexyl; 4-methylcyc1ohexyl; vinyl; propenyl (1); propenyl (2); phenylethenyl; benzyl; ,8- phenylethyl; 0c phenylpropyl; phenylethenyl, benzyl, ,8- phenylethyl, or a-phenylpropyl substituted by a member of the group consisting of halogen, lower alkyl of 1-6 carbon atoms, alkoxy of l-6 carbon atoms, carboxylalkyl of 1-6 carbon atoms in the alkyl group, and cyano; phenyl; phenyl substituted by a member of the group consisting of halogen, lower alkyl of l-6 carbon atoms, lower alkyl of 1-6 carbon atoms substituted by a member of the group' consisting of halogen, alkoxy of l-6 carbon atoms, cyano, and carboxyalkyl of l-6 carbon atoms in the alkyl group, alkoxy of l6 carbon atoms, alkoxy of l-6 carbon atoms substituted by a member of the group consisting of halotriazinyl, oxazinyl, morpholinyl, thiazinyl, benzopyrrolyl, benzimidazolyl, benzthiazolyl, quinolinyl, quinoxalinyl.

2. The anthraquinone dyestuffs of claim 1, in which said anthraquinone radical contains 3 or 4 condensed rings.

3. A dyestufi of claim 1: /3-(l-anthraquinonylamino)-otcyanoacrylic acid morpholide.

4. A dyestulf of claim 1: ,8-(1-anthraquinonylatmino)-ucyanoacrylic acid piperidide.

5. A dyestutf of claim 1: B-(4-hydroxy-l-anthraquinonylamino)-acyanoacrylic acid morpholide.

6. A dyestulf of claim 1: [3-(4-methoxy-l-anthaquinonylamino)-u-cy anoacrylic acid morpholide.

7. A dyestuff of claim 1: fi-(4-phenylamino-l-anthraquinonylamino)-ot-cyanoacrylic acid morpholide.

8. A dyestuff of claim 1: fi-(4-p-methoxyphenylaminol-anthraquinonylamino)-ct-cyanoacrylic acid morpholide.

'9. A dyestuff of claim 1: fl-(4p-methylpheny1amino-1- anthraquinonylaminoya-cyanoacrylic acid morpholide.

10. A dyestufi of claim 1: {3-(l-anthraquinony1amino)- a-cyanoacrylic acid amide.

11. A process for the production of an anthraquinone dyestuff of claim 1 which comprises reacting at 0-250 C. a cyanoacetic acid amide of the formula:

wherein R and R have the meaning given in claim 1, in the presence of an acid-binding agent selected from the group consisting of alkali metal oxide, alkali metal hydroxide, alkaline earth metal oxide, alkaline earth metal hydroxide, salt of an alkali metal or alkaline earth metal with a weak inorganic or organic acid, tertiary organic base, and alcoholate of an alkali metal or an alkaline earth metal, with an N-anthraquinonyl-N'-formamidinium salt of the formula:

R A -N H- CH=N R4 11 wherein A is an anthraquinone radical; X is an anion; n is an integer from 1 to 4; and R and R are selected from the group consisting of hydrogen, lower alkyl of 1-6 carbon atoms, phenyl, phenyl substituted with a member of the group consisting of chlorine, bromine, and lower alkyl of 1-6 carbon atoms, and R and R may be alkylene of 1-6 carbon atoms when combined with N in the above formula and 02 additional heteroatoms selected from the group consisting of O, N, and S to form a cyclic structure.

12. The process of claim 11, in which the said anthraquinone radical contains 3 or 4 condensed rings.

13. The process of claim 11 wherein the reaction takes place in an organic solvent as a reaction medium.

References Cited OTHER REFERENCES Chemical Abstracts, vol. 57, col. 3591 (1962) (Abstract of Sivasankaran et a1.)

Karrer, Organic Chemistry, 4th English Ed., page 928, Elsevier Pub. Co. (N.Y.) 1950.

JOHN D. RANDOLPH, Primary Examiner US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. ,49l Dated 1971 Inven Rutcrer Neeff It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

4 2nd formula should be 4 I 6th formula "CO-Y" should be COX COLUMN LINE m L 2nd Formula "CH=N" should be -CH=CN-- 2 31 "each which" should be each of which---.

3 6th formula "X=H" should be --X-H--.

3 6th formula "-OCH O-;" should be Page 2 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,5 0,491 D te Feb 2. 1971 Inventor(s) Rutqer Neeff It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

COLUMN LINE ERROR CH3 4 7th formula N 5 3rd formula "X=H,CH3,C2H2,C3H7

should be X=II,CH3,-C2H2,-C3H7 5 4th formula "NHCH=N(CH l" should be NH-CH=N (cn l 6 7th formula "x=H" should be X=H--.

8 61 "dimethy" should be dimet UNITED STATES PATENT OFFICE Page 3 CERTIFICATE OF CORRECTION Patent No. 3 r v 491 Dated Feb 2 I 1971 It is certified that error appears in the above-identified uatent and that said Letters Patent are hereby corrected as shown below:

COLUMN LINE ERROR 10 65 "carbinet" should be -cabinet-.

13 24 "bias" should be -bis---.

13 29 "a" should be 13 46 "the" should be -there--.

14 45 "0, 10.01%" should be 14 59-60 "the 4-ethoxy benxyl-amide" should be the 4-ethoxy benzylamide-.

15 46-47 "cyclohexyamide" should be cyclohexylamide---.

l6 ll-l2 "anthraquinonyl" should be anthraquinonyl) 18 Ex. 34 "anthraquinonylamino" should be anthraquinonylamino) 19 46 I "4-methyl-analide" should be 4-methylanilide-.

Signed and sealed this 19th day of October 1971.

(SEAL) Attest:

EDWARD M.FLETCHER,'J'R. ROBERT GOTISCHALK Attesting Officer Acting Commissioner of 

